Accepted Manuscript

Title: Self-Healing, antibacterial and sensing nanoparticle

coating and its excellent optical applications

Authors: Hongyun Xuan, Wei Dai, Yanxi Zhu, Jiaoyu Ren,

Jianhao Zhang, Liqin Ge

PII: S0925-4005(17)32209-8
DOI: https://doi.org/10.1016/j.snb.2017.11.078
Reference: SNB 23572

To appear in: Sensors and Actuators B

Received date: 8-8-2017

Revised date: 15-11-2017
Accepted date: 15-11-2017

Please cite this article as: Hongyun Xuan, Wei Dai, Yanxi Zhu, Jiaoyu Ren,
Jianhao Zhang, Liqin Ge, Self-Healing, antibacterial and sensing nanoparticle
coating and its excellent optical applications, Sensors and Actuators B:
Chemical https://doi.org/10.1016/j.snb.2017.11.078

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 Self-Healing, antibacterial and sensing nanoparticle coating and its

excellent optical applications

Hongyun Xuana, Wei Daia, Yanxi Zhuc, Jiaoyu Rena, Jianhao Zhangb, Liqin Gea,*

a
National Demonstration Center for Experimental Biomedical Engineering Education,
State Key Laboratory of Bioelectronics, School of Biological Science and Medical
Engineering, School of Biological Science and Medical Engineering, Southeast

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University, Nanjing 210096, P.R. China

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b
Nanjing Center of Meat Quality and Safety Control, Key Lab of Meat Processing
and Quality Control, Ministry of Education, College of Food Science, Nanjing

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agricultural university, Nanjing 210096,P.R.China.
c
Central Laboratory of Linyi People’s Hospital, Linyi 276003, PR China.

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* E-mail: lqge@seu.edu.cn.

In our paper, the main highlights are as follows: U

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 Develop novel nanoparticle packaging materials by layer-by-layer self-assembly
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technique.
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 Prepared nanoparticle coatings can heal the damages during use and prolong the
service time.
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 MoS2 is used to not only improve coatings’ antimicrobial property but also endow
them metal ions sensing property.
E PT

Abstract: Self-healing, antibacterial and metal-ion sensing coatings with

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nanoparticles were developed using layer-by-layer (LbL) self-assembly technique via

host-guest interaction. The coatings consist of MoS2 nanosheets, beta-cyclodextrin
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(β-CD)-modified poly (ethylenimine) (PEI) and adamantane (AD)-modified poly

(acrylic acid) (PAA). Damages to conventional coatings results in cracking and affects
the coatings’ ability to maintain antibacterial and sensing qualities. The prepared
MoS2/β-CD-PEI/AD-PAA self-healing coatings are not only able to greatly suppress
bacterial adhesion and have excellent antibacterial property, particularly under UV
light irradiation, but also have a longtime service time. Moreover, the self-healing
coatings first applied the fluorescence quenching for detecting heavy metals (Co2+).
Fluorescence spectra demonstrated that a linear relationship existed between the
fluorescence intensity and the Co2+ concentration with 0 ~ 0.1 ug/mL and the
detection limit of Co2+ is 0.018 mg/mL. Therefore, the nanoparticle multilayer
polyelectrolyte hybrid coatings have a potential application in food industries.

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Keywords: antibacterial, self-healing, LbL assembly, host-guest interactions, Co2+

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senor

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1. Introduction
Inspired by nature, self-healing materials have an attracted considerable interest

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in various fields such as biomedical engineering, [1] chemical engineering [2] and food
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[3]
engineering. Therefore, all kinds of self-healing materials, ranging from solid
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[4-5]
concrete to soft elastomers, have been introduced. In recent years, self-healing
coatings as a new type of self-healing material has become a unique and popular topic.
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Some recent studies dealt with the self-healing coatings and showed how covalent or
[4, 6-7]
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noncovalent interactions play an important role in demonstrating such behavior.

[8] [9] [10]
Besides, Schiff base, hydrogen bonding, and host-gust interactions are
[11]
assumed to be responsible for the self-healing behavior observed. Sun et al. and
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Zhu et al. [12] have reported the hydrogen bonding coatings that exhibited repeatable
self-healing and easy processability. When a supramolecular assembly approach is
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followed, the host-guest coatings exhibit not only repeatable self-healing and easy
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processability but also excellent mechanical and acid-resistant properties. [10, 13] Based
on the previous study of the self-healing host-guest coatings, [10] their antimicrobial
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and sensing properties have been further developed.

Recently, the environmental safety assessment of nanomaterials has attracted the
[14-15]
interest of many scientists in various fields. In the fields of biomedical
engineering, it has been discovered that the coatings soaked in complex body fluid are
vulnerable to microorganism accumulation, which will not only block circulation of
biomolecules and metabolites but also cause inflammatory responses. [16-17] And in the
fields of food engineering, specifically delivery and the storage of fresh fruits and
vegetables, scientists found that coatings can grow bacteria that causes the
deterioration of fruits and vegetables under humid conditions. [18] Recently, to address
these issues, the reported coatings have been endowed with antimicrobial properties
through the inclusion of TiO2 nanoparticles into one structure loading and the
[19-20]
releasing of antibiotics in the microcapsules. They cannot be repeatedly used

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and self-healed; Therefore, Molybdenum disulfide (MoS2) is first introduced to

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endow the coatings with simultaneous antimicrobial and self-healing properties, and

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other properties are also developed to expand the application fields.

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MoS2 that is a typical layered crystal like a graphene structure, has shown great
promise and has been investigated with great attention. [21] However, MoS2 nanosheets

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possess excellent biocompatibility and photoluminescence characteristics comparing
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[22-23]
with bulk MoS2. The increasingly broad application of MoS2 leads to contact
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[24]
with environmental microorganisms and photoluminescence sensors. Nilam et al.
[25]
and Marek kostecki et al. have demonstrated that MoS2 nanosheets have
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antibacterial and antifungal properties, respectively. Moreover, strong

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photoluminescence can emerge from MoS2 nanosheets because its band gap can reach
[26]
1.9 eV for a single monolayer. And its photoluminescence relies on the transition
from indirect band gap to direct band gap. In addition, as an attractive semiconductor
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material, MoS2 can be applied in the flexible substrate due to a large in-plane carrier
mobility of about 200-500 cm2/ (Vs) and robust mechanical properties. [27]
Goki Eda
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et al. have deposited the thin film of MoS2 on flexible PET. [28] Our work shows that
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MoS2 with the biocompatibility and photoluminescent properties is successfully

fabricated on the flexible host-guest coatings to form the self-healing MoS2/host-guest
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hybrid coatings, and that, the coatings have specific response to heavy metal ions
Co2+.
Heavy metals in biological fluids and food engineering are a major source of
pollution. Excessive amounts of heavy metals could lead to chronic toxicity and
[29]
become harmful to human health. As a primary micronutrient, Co2+ is required
 [30]
for the growth of plants and animals. Co2+ is also a part of vitamin B12 that human
body can’t synthesize. Humans do need to ingest this micronutrient (found in foods
[31]
such as eggs, fish, milk and green vegetables), but, large amounts of Co2+ can
[32]
generate toxicological effects in human body. Therefore, determination of Co2+
concentration is essential and significant. Up to now, several methods have been
employed to detect Co2+ concentration. [33-34]
But pretreatment steps for modification
and functionalization of a sorbent are so complicated. MoS2 nanosheets with layered

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structure and abundant sulfur groups on the edges and surfaces can greatly absorb

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Co2+ and are applied in heavy metals sensing. Only, Shemirani et al. employed MoS2

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nanosheets to defect Co2+ in vegetable and water samples. [35]
In our work, however,

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the fluorescence quenching was first investigated between Co2+ concentration and
MoS2 to successfully fabricate the sensing coatings for Co2+. Taking into account its

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damage failure, the self-healing sensing coatings were carried out.
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Herein, to achieve antibacterial and self-healing coatings, the
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MoS2/β-CD-PEI/AD-PAA coatings were successfully fabricated on the substrate via
LbL self-assembly technique (Scheme 1). Besides, the photocatalytic disinfection
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activity of MoS2 nanosheets was introduced to achieve better disinfection effect. And,
the photoluminescence property was firstly applied in Co2+ sensor. Then,
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MoS2/(β-CD-PEI/AD-PAA) 15 coatings were characterized by scanning electron

microscope (SEM) and UV-vis absorption spectrum. The self-healing process was
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observed by SEM, optical microscope and semiconductor characterization system.

The coatings’ antibacterial effects in the presence or absence of UV irradiation were
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systematically investigated. Due to absorption, large surface area and strong

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photocatalytic property, the coatings exhibited higher photocatalytic sterilization and

bacteria removal efficiency under UV irradiation. Moreover, a linear relationship
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between the fluorescence intensity and the Co2+ concentration was demonstrated by
fluorescence spectra.

2. EXPERIMENTAL SECTION

2.1 Materials
 poly ( acrylic acid ) ( PAA ) ( Mw ≈ 450000 g.mol-1 ), Poly ( ethylenimine ) ( PEI )
( Mw ≈ 25000 g.mol-1 ), 1-rthyl-3-( 3 ( dimethylamino ) propyl ) carbodiimide,
ammonium polyphosphate, hydrochloride ( EDC ) and N-hydroxysuccinimide ( NHS )
were purchased from Sigma-Aldrich. Adamantanamine (AD) and Carboxymethyl
beta-cyclodextrin (β-CD) were respectively obtained from Shanghai mindray
chemical technology co., LTD and Shandong binzhou wisdom source biotechnology
co., LTD. Cobalt ions and dialysis bag was bought from Nanjing yat sen villa glass

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instrument co., LTD. The emerald-green solution of Molybdenum disulfide (MoS2)

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flakes (100-400 nm, 18 mg/ mL) was bought from Graphene Supermarket.

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Dihydrogen phosphate and disodium hydrogenorthophosphate were all purchased

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from Nanjing yat sen villa glass instrument co., LTD to perpetrate pH 8.0 phosphate
buffered saline (PBS). Fetal bovine serum (FBS), Dulbecco’s modified eagle’s

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medium (DMEM), and L929 cells were bought from Biotechnology Center (Nanjing,
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Ge man).
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2.2 Characterization
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Zeiss Ultra Plus field emission scanning electron microscope (SEM)

(Zeiss, Oberkochen, Germany) was used to obtain the surface morphology of
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the prepared samples. The self-healing process of the samples on the substrate
was observed with SEM and Microscope (OLYMPUS BX51). Fluorescence
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spectra were measured with fluorescent Inverted microscope (OLYMPUS IX71),

which was equipped with a fiber optic spectrometer (Ocean Optics, QE65000). The
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typical current−voltage (I−V) measurements and imaging were carried out using
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an RHK Technology-100 STM system in ultrahigh vacuum with platinum

conductive probes.
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2.3 Fabrication self-healing, antibacterial and metal-ion sensing coatings via LbL

assembly technique

Synthesis of β-CD-bearing PEI and AD-modified PAA polymer and the

preparation of dealing substrate have been reported in the previous work.[10,13] The
aqueous solutions of AD-PAA and β-CD-PEI were alternately deposited on the
substrate to obtain the (PAA-AD/PEI-β-CD) n coatings based on host-guest
interaction. Then, MoS2 solution was spin-coated onto the (PAA-AD/PEI-β-CD) n
coatings at 1000 rpm for 60s. Finally, the self-healing MoS2/β-CD-PEI/AD-PAA
hybrid coatings were successfully obtained via LbL assembly technique.

2.4 Cell Viability Studies

The MoS2/(PAA-AD/PEI-β-CD) 15 coatings were attached to 6-well cell culture

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[36]
plates . Then, the L929 cells were cultured in 6-well cell culture plates at 5x105

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cells per well in 90% DMEM and 10% FBS and incubated at 37 ℃ in a 5% CO2 / 95%
O2 atmosphere for 48 h. Finally, the L929 cells on the coatings were observed by the

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inverted microscope to evaluate the cell viability.

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2.5 Antibacterial Activity

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As a model bacterial strain, gram-negative Escherichia coli aw1.7 (E.coli) was
employed to evaluate the antimicrobial properties of the coatings. E.coli were
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incubated in nutrient broth at 37 ℃ for 24 h to yield a cell count of approximately 109
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colony forming units (CFU) / mL. Then 50 μL bacterial solution was respectively
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added on the surfaces of the glass substrate and the MoS2/(PAA-AD/PEI-β-CD) 15

coatings. They were incubated at 37 ℃ for 1 h after irradiated by UV light for 30 mins.
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Then the coatings with the bacterial solution were cleaned with 5 mL of sterile 0.85%
(wt / vol) saline solution. The cleanout fluid was carefully pipette out, and bacteria
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concentrations were determined by the standard plate count method. The plates were
incubated at 37 ℃ for 24 h. The number of colonies was enumerated through visual
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inspection. The glass substrate and the MoS2/(PAA-AD/PEI-β-CD) 15 coatings were

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carried out in the absence of a photocatalyst as the light control group.

3. RESULTS AND DISCUSSION

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The surface morphology of the MoS2/(PAA-AD/PEI-β-CD) 15 coatings was

characterized with SEM and UV-vis spectra. It is illustrated that the MoS2 could be
successfully coated on the surface of the (PAA-AD/PEI-β-CD) 15 coatings by the
spin-coating method. As shown in the SEM image (Figure 1a), the surface protrusions
could be clearly seen on the surface morphology of the MoS2/(PAA-AD/PEI-β-CD)
15 coatings. And, the plane size of the MoS2 flakes ranged from 100 nm to 400 nm,
according to the information provided by the manufacturer. The UV-vis spectrum was
used to demonstrate that the MoS2 was self-formed on the coatings and the
obtained coatings had the photoluminescence property. The absorption peaks at
~300 nm and between 600~700 nm (Figure 1c) could be owed to the excitonic
features of the MoS2 nanosheets. [37-38] The direct excitonic transitions at the K point
of the Brillouin zone[38] were reflected in photoluminescence spectra of the

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MoS2/(PAA-AD/PEI-β-CD) coatings, which exhibited the emission characteristic

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15

peak at ~500 nm (Figure 6c). What’s more, their contact angle was about 98.02 ℃ as

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shown in Figure 1d, which describes that the coatings possess an excellent

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hydrophobic surface. The data above clearly indicates the MoS2/(PAA-AD/PEI-β-CD)

15 coatings were self-assembled successfully, which make it possible to be employed

antibacterial sensor in the following experiments.
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Figure 2, S1 shows the self-healing process images of the
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MoS2/(PAA-AD/PEI-β-CD) 15 coatings that were self-healed immediately after
[10, 39]
scratching. The possible self-healing mechanism is as follows: the
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interface of the scar is swollen when exposed to moisture; the swollen

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interfaces are then joined with each other and the host–guest interaction is
formed again. The self-healing process is thus completed. Figure 2a shows that
the width of the scar was 20 μm after scratching. Then, host-guest complexes were
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formed again when the scar interface was more closely contacted for 30 mins
with the evaporation of water. Finally, the scar healed successfully, recovering the
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initial coatings (Figure 2b). In order to further investigate the self-healing process of
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the MoS2/(PAA-AD/PEI-β-CD) 15 coatings, the typical current−voltage (I−V) image

was employed. The MoS2/(PAA-AD/PEI-β-CD) 15 coatings were deposited on the
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ITO substrate, as per the samples. In Figure 2c, their typical I−V curves of the
self-healing process showed the linear (ohmic) characteristics. The ohmic value of the
initial coatings was 48.9 Ω. Due to the ITO surface exposed to air after scratching, the
current obviously increased and the ohmic value was 40.2 Ω. However, the I−V curve
after the self-healing process was almost restored to the initial state and its ohmic
value was 49.5 Ω. This shows that the scar healed successfully and the
MoS2/(PAA-AD/PEI-β-CD) 15 coatings exhibited their admirable self-healing
capacity.
As shown in Figure 3a-c, the MoS2/(PAA-AD/PEI-β-CD) 15 coatings were able
to kill E.coli with more than 65.7% reduction in bacterial counts. Moreover, the
MoS2/(PAA-AD/PEI-β-CD) 15 coatings displayed the good biocompatibility in
Figure S2. [40] These indicate that MoS2 nanosheets had the antibacterial effect in the

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[41]
dark, which was in accordance with Na Wu’s results. The coatings displayed a

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mild direct cytotoxicity because of its excellent hydrophobic surface, [42-43] which

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shown in Figure 1d. MoS2 nanosheets had a larger surface area than bulk MoS2.

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Furthermore, MoS2 nanosheets could penetrate cell walls to damage the cell
membranes and increase the reactive oxygen species that reduces membrane stability.
[44-45]

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In order to further research, SEM was utilized to observe the E. coli morphology
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on the coatings’ surface (Figure S3). Some E. coli changed in structure (i.e., they
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shrunk) and their membranes appeared to be broken. These results were similar to the
observations reported for other nanomaterials. [41, 46-47]
As a result, without UV
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irradiation, the MoS2/(PAA-AD/PEI-β-CD) 15 coatings possess a better antibacterial

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property than the bare glass substrate.

In general, due to the narrow band gap of the MoS2, the electrons (e-) and holes
(h+) were generated when the surface of the MoS2 was illuminated by light energy.
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The h+, HO·, H2O2, and O2- were usually considered to be the reactive oxidative
[48]
species responsible for the bactericidal activity. Understanding which species
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played the most remarkable role was important in affecting the microbial environment.
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The related photocatalytic reactions about the MoS2 could be summarized by the
following: [49-50]
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MoS2 + hv → MoS2 (e-, h+) (1)

e- + h+ → hv (2)
h+ + OH- → HO· (3)
h+ + H2O2 → HO· + H+ (4)
e- + O2 → O2- (5)
 Due to the photogenerated electron-hole pairs, the photocatalytic reactions on the
MoS2 surface could influence the microbial environment to inhibit the bacterial
growth. Photoluminescence spectra were conducted to investigate the migration,
transfer, and recombination processes of the photogenerated electron-hole pairs. The
photoluminescence spectra of MoS2 nanosheets in Figure 4c exhibited that the
emission bands positioned at 475-500 nm. As shown in Figure 4a, b, the coatings
showed an antibacterial effect toward E.coli. Under UV light irradiation, the

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MoS2/β-CD-PEI/AD-PAA coatings vastly improved their antibacterial property,

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which was able to reach 100% (Figure 4d). Because the MoS2 surface increased the

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more reactive oxygen species (h+, HO·, H2O2, and O2-) under UV light irradiation,

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particularly, the HO·, H2O2 and O2- would reduce membrane stability and damage the
membrane. Therefore, the MoS2/(PAA-AD/PEI-β-CD) 15 coatings have the

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completely antibacterial property under UV light irradiation. Taking into account its
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high antibacterial activity, the coatings are ideal for advanced pathogenic bacteria
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wastewater treatment and fresh storage of fresh fruits and vegetables.
To investigate the quenching ability of Co2+ towards the
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MoS2/(PAA-AD/PEI-β-CD) 15 coatings and acquire the best sensing for Co2+, the
Co2+ analysis is recorded by fluorescence spectrophotometer. In order to absorb more
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Co2+, the pH value and contact time were investigated. Recently, Shemirani et al.
have found that MoS2 nanosheets had the best adsorption capacity of Co2+ when they
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were immersed in the Co2+ solution (pH 8.0) for 20 mins. [35, 38]
Therefore, according
to the above conditions, the experiment exploring the hypothesis that the coatings
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could detect Co2+ by the fluorescence quenching method had been completed for the
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first time. The results were shown in Figure 5. By adding the different Co2+
concentration, the fluorescent intensity of the coatings exhibited a decreasing process
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as shown in Figure 5a. Co2+ ions were absorbed on the surface of the
MoS2/(PAA-AD/PEI-β-CD) 15 coatings to induce energy transition. The quenching
efficiency E was calculated according to the formula blow: [51-52]
F0 − F
E= × 100%
F0
 where F0 and F were the fluorescence intensities in the absence and the presence
of Co2+. The ultimate quenching efficiency of the MoS2/(PAA-AD/PEI-β-CD) 15

coatings reached 77.4% when the final Co2+ concentration was 0.1 μg/mL. Along with
the increase of the Co2+ concentration from 0 to 0.1 μg/mL, a gradual reduction of the
fluorescence peak centered at 500 nm could be observed in Figure 5a. Figure 5b
shows the curve obtained with the fluorescence intensity versus the Co2+
concentration. A high correlation (R2 = 0.993) was achieved in the Co2+ concentration.

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The Co2+ sensing system demonstrated a limit of detection of 0.018 mg/mL and a

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dynamic range over 0 ~ 0.1 μg/mL. The results clearly demonstrate that the

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MoS2/(PAA-AD/PEI-β-CD) 15 coatings could be applied as a sensing platform for the

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detection of Co2+.
Moreover, the effect of the Co2+ concentration on the self-healing ability was

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investigated. These results found that the MoS2/(PAA-AD/PEI-β-CD) 15 coatings had
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good self-healing properties and recovered the original plain coatings in the different
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Co2+ concentration, as shown in Figure S4 (a, b,…f). It could be inferred that the
host-guest interaction between PEI-β-CD and AD-PAA improved the assembled
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ability to make the film more stable. According to the result shown in Figure S4, the
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MoS2/(PAA-AD/PEI-β-CD) 15 coatings were all fairly stable and healed. A

conclusion can be made that coatings based on the host-guest interaction were
stable, and self-healing capability was not affected by the Co2+ concentration.
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Therefore, their sensitivity will not be influenced when the self-healing

coatings are damaged in work.
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In pathogenic bacteria wastewater, fruits and vegetables, Co2+ was the common
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coexistence of other heavy metals, such as Ca2+, Fe2+, Mg2+, Li+ and so on. In
our research, the MoS2/(PAA-AD/PEI-β-CD) 15 coatings were provided with
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selectivity to Co2+ and were evaluated by testing their response to other

environmentally relevant metal ions, such as Ca2+, Fe2+, Mg2+, and Li+ at a
concentration of 15 μg/mL. Only the solution of Co2+ (0.1 μg/mL) could induce
the fluoresce intensity to vastly shift. In sharp contrast, the other metal ions
hardly had any effect (Figure 6). Therefore, the MoS2/(PAA-AD/PEI-β-CD)15
coatings exhibit good selectivity to Co2+ against other associated metal ions and
imply the probability of their use in actual samples.
INCLUTION
The self-healing MoS2/(PAA-AD/PEI-β-CD) 15 coatings based on host–guest
interaction are prepared on the various substrates via LbL assembly for antibacterial
and sensing applications. The self-healing properties of the
MoS2/(PAA-AD/PEI-β-CD) 15 coatings are characterized by SEM and I−V image. It

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could be found that the coatings exhibited so admirable self-healing capacity;

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meanwhile their antibacterial property was investigated. Under UV light irradiation,

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the self-healing coatings exhibited the superior antibacterial efficiency, which was due

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to the unique heterojunction in the MoS2 nanosheets. Their antibacterial properties
are able to reach 100%. Besides, the self-healing coatings first applied the

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fluorescence quenching for detecting the heavy metals. A Co2+ detection platform was
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established with a limit of 0.018 mg/mL and a dynamic range over 0 μg/mL to 0.1
μg/mL. This simple and easy approach to preparing the self-healing coatings with
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antibacterial and sensing properties offers unique development opportunities in the

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field of highly engineered materials, such as food packaging, for which safety,
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performance, and longer fatigue life are crucial smart factors.

ACKNOWLEDGEMENTS
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H. Xuan thanks for support by the scientific research foundation of graduate

school of southeast university (YBJJ1723). Prof. Dr. Ge thanks for the financial
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support from 12th five-year national science and technology support plan corpus
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(2015BAD16B05-5), Jiangsu province agricultural science and technology innovation

fund projects (CX (15)1049), and Testing of the large-scale Apparatus from the
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Southeast University. Prof. Dr. Ge also thanks for the support from Prof. Dr. Gu
Zhongze's group.
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Author biographies

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Liqin Ge

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Title: Pro.
Affiliation, Country: State Key Laboratory of Bioelectronics, School of Biological

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Science and Medical Engineering, Southeast University, Nanjing, P.R. China
Phone: +86-025-83795632 Fax: +86-025-83795632-809 E-mail: lqge@seu.edu.cn

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Prof. Ge is currently a professor in southeast university and mainly researches

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polymer and self-assembly functional materials. She graduated from Chinese
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Academy of Sciences Institute of Chemistry in 2003 year and received a doctorate
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that was the jointly training of the two institutes of Chinese Academy of Sciences and
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Germany Mapu collogen and interface. She went to McGill University in Canada for
postdoctoral research. Moreover, she has received the following projects:
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(1) National natural science foundation

(2) CUP cooperation projects of China and Japan
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(3) Southeast University Outstanding Young Teachers Funding Scheme /

NSFC Pre-Research Fund
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(4) National major research institutes

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In recently years, prof. Ge has published many articles about the self-healing
multi-functional coatings in SCI journal.
[1] H. Y. Xuan, J. Y. Ren, X. Z. Wang, J.H. Zhang, L. Q. Ge. Flame-retardant, non-irritating and
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self-healing multilayer films with double-network structure. Composites Science and

Technology, 2017, 145, 15-23.
[2] H. Y. Xuan, J. Y. Ren, J. H. Zhang, L. Q. Ge. Novel highly-flexible, acid-resistant and
self-healing host-guest transparent multilayer films. Applied Surface Science. 2017, 411, 303-314.
[3] H. Y. Xuan, J. Y. Ren,Y. X. Zhu, B. Zhao, L. Q. Ge. Aptamer-functionalized P(NIPAM-AA)
hydrogel fabricated one-dimensional photonic crystals (1DPCs) colorimetric sensing, RSC Adv,
2016, 6, 36827-36833.
[4] Y. X. Zhu, H. Y. Xuan, J. Y. Ren, L. Q. Ge. Self-healing multilayer polyelectrolyte composite
film with chitosan and poly (acrylic acid) [J]. Soft Matter, 2015, 11(43): 8452-8459.
[5] H. Y. Xuan, J. Y. Ren, Y. X. Zhu, X. F. Liu, L. Q. Ge. A green method to fabricate uniform
porous responsive one-dimensional photonic crystals, Colloids and surfaces A, 2016, 507, 83-88.
[6] H. Y. Xuan, C. Yao, X. L. Hao, C. H. Liu, J. Y. Ren, Y. X. Zhu, L. Q. Ge. Fluorescence
enhancement with one-dimensional photonic crystals/nanoscaled ZnO composite thin films,
Colloids and surfaces A, 2016, 497, 251-256.
[7] Y. X. Zhu, H. Y. Xuan, J. Y. Ren, X. F. Liu, L. Q. Ge, Color Tunable Ultrathin Films Capable
of Healing Multiple Scratches[J]. ChemNanoMat, 2016, 2(8):791–795.
[8]Y. X. Zhu, H. Y. Xuan, J. Y. Ren, Bo Zhao, L. Q. Ge, Humidity responsive self-healing based

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on intermolecular hydrogen bonding and metal–ligand coordination[J]. RSC Advances, 2016,

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6(92): 89757-89763.
[9] J. Y. Ren, H. Y. Xuan, Y. X. Zhu, X. F. Liu, L. Q. Ge. Beta-glucan quantification by

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fluorescence analysis using photonic crystals. RSC Adv, 2016, 6, 32286-322895.
[10] J. Y. Ren, H. Y. Xuan, C. H. Liu, C. Yao, Y. X. Zhu, X. F. Liu, L. Q. Ge. Graphene oxide

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hydrogel improved sensitivity in one-dimensional photonic crystals for detection of beta-glucan.
RSC Adv, 2015, 5, 77211-77216.
[11] J. Y. Ren, H. Y. Xuan, L. Q. Ge. Colorful self-healing polyelectrolyte nano-film based on

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Schiff base linkage capable of sensing. European Polymer Journal, 2017, 93, 521–529.
[12] Y. X. Zhu, C. Yao, J. Y. Ren, C. H. Liu, L. Q. Ge. Graphene improved electrochemical
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property in self-healing multilayer polyelectrolyte film [J]. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 2015, 465: 26-31.
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Figure 1. (a, b) SEM images of the MoS2 nanosheets coated on the
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(PAA-AD/PEI-β-CD) 15 coatings; (c) UV-vis absorption spectrum of the
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MoS2/(PAA-AD/PEI-β-CD) 15 coatings; (d) contact angle of the

MoS2/(PAA-AD/PEI-β-CD) 15 coatings
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Figure 2. Self-healing process images of the MoS2/(PAA-AD/PEI-β-CD) 15

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coatings via LbL self-assembly: (a, b) SEM ; c) I−V curves of the
MoS2/(PAA-AD/PEI-β-CD) 15 coatings during the self-healing process
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Figure 3. (a, b) Images of E.coli colonies on agar plates (a) the glass substrate (b)
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the MoS2/(PAA-AD/PEI-β-CD) 15 coatings; (c) Colony forming units (CFUs) of

E.coli colonies without UV irradiation in the glass substrate (Blank) and the
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MoS2/(PAA-AD/PEI-β-CD) 15 coatings (Treated)

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Figure 4. (a, b) Images of E.coli colonies on agar plates (a) the glass substrate (b)
the MoS2/(PAA-AD/PEI-β-CD) 15 coatings; (c) Photoluminescence spectra of the
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coatings recorded under UV light irradiation. The characteristic peak at ~500 nm is

clearly seen; (d) Colony forming units (CFUs) of E.coli colonies with UV irradiation
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in glass substrate (Blank1) and MoS2/(PAA-AD/PEI-β-CD) 15 coatings (Treated1)

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Figure 5. a) Fluorescence spectra of the MoS2/(PAA-AD/PEI-β-CD) 15 coatings

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after the addition of 0 ~ 0.1 μg/mL Co2+ (pH 8.0); b) calibration curve achieved with
the fluorescence intensity versus the Co2+ concentration

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Figure 6. The effect of various metal ions on the self-healing coatings sensors
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fluorescence intensity shift. (0.1 μg/mL for Co2+ and 15 μg/mL for Ca2+, Fe2+,
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Mg2+, Li+)
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Scheme 1. Schematic of the
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preparation of the self-healing
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MoS2/β-CD-PEI/AD-PAA antibacterial coatings via LbL assembly, with dynamic
cross-linked formation generated based on guest–host complexation of β-CD
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and AD.
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